WO2009113412A1 - Composition d'émulsion contenant un isocyanate bloqué, procédé pour produire celle-ci, couche primaire à base aqueuse pour substrat poreux, et composition de revêtement au four à base aqueuse - Google Patents

Composition d'émulsion contenant un isocyanate bloqué, procédé pour produire celle-ci, couche primaire à base aqueuse pour substrat poreux, et composition de revêtement au four à base aqueuse Download PDF

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WO2009113412A1
WO2009113412A1 PCT/JP2009/053707 JP2009053707W WO2009113412A1 WO 2009113412 A1 WO2009113412 A1 WO 2009113412A1 JP 2009053707 W JP2009053707 W JP 2009053707W WO 2009113412 A1 WO2009113412 A1 WO 2009113412A1
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isocyanate
emulsion composition
blocked isocyanate
emulsion
blocked
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PCT/JP2009/053707
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English (en)
Japanese (ja)
Inventor
孝喜 城野
直考 泉
育 大木
悌久 沖山
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日本ポリウレタン工業株式会社
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Priority to JP2010502765A priority Critical patent/JP5299420B2/ja
Publication of WO2009113412A1 publication Critical patent/WO2009113412A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to a blocked isocyanate-containing emulsion composition, a method for producing the same, an aqueous base treatment agent for a porous substrate, and an aqueous baking type coating composition. More specifically, the emulsion forms a core-shell structure and has a small particle size distribution. By narrowing, it is related to the emulsion composition with excellent water dispersibility and storage stability at room temperature and above, and good performance as a coating agent, etc. In addition, the present invention relates to an aqueous base treatment agent for a porous substrate and an aqueous baking type coating composition which are excellent in coating film performance and the like.
  • Polyurethane resin compositions are used extensively as coating agents (coating agents), and are widely used as paints in various industrial fields such as vehicles, building materials, home appliances, and furniture.
  • a coating agent has been emphasized as an aqueous (aqueous) composition that does not use an organic solvent from the viewpoints of environmental protection against air and wastewater and work safety in the manufacturing process and implementation. Since it is not used, it is economically advantageous, and is being used more frequently than organic solvent-based compositions.
  • water-based polyurethane resin coatings generally have lower physical properties such as durability and solvent resistance than organic solvent-based coatings, so that various physical properties equivalent to organic solvent-based coatings can be obtained. Consideration of improvement is continued.
  • an aqueous polyurethane resin composition generally, dispersibility in an aqueous medium is low, and storage stability is insufficient due to high reactivity of an isocyanate group with water. Therefore, improvement of these performances is also important. Yes.
  • the isocyanate group-terminated urethane prepolymer introduced with a carboxyl group is neutralized to be water-dispersible.
  • a polyurethane emulsion for an aqueous one-component coating agent containing a urethane prepolymer emulsified in water and subjected to a chain extension reaction and a urethane prepolymer that is incompatible with water is presented (see Patent Document 1). Even if the water dispersibility is improved, the coating properties of the coating agent as a whole are still not sufficient.
  • an aqueous one-component polyurethane resin coating agent using a so-called blocked isocyanate compound is well known (for example, see Patent Document 2).
  • This type of coating is a so-called one-component baking type coating in which the isocyanate group is blocked (blocked) so that crosslinking curing does not proceed at room temperature, and the block of the isocyanate group is removed by heating and the coating layer is cured.
  • the storage stability is improved, and the coating layer is generally better in various properties such as water resistance, solvent resistance, durability and adhesion than those of a room temperature dry type.
  • a baking type water-based block polyurethane coating using an isocyanate compound having a nonionic hydrophilic group and an ionic surfactant is also known (see Patent Document 3).
  • Patent Document 3 a baking type water-based block polyurethane coating using an isocyanate compound having a nonionic hydrophilic group and an ionic surfactant.
  • these blocked isocyanate-based baking polyurethane coatings still have sufficient durability, solvent resistance, impact resistance, glossiness, etc. compared to organic solvent-based coatings. Furthermore, water dispersibility and storage stability are not fully satisfied.
  • a non-anionic (nonionic) polyisocyanate is mixed with a carboxyl group-introduced isocyanate group-terminated urethane prepolymer, all isocyanate groups in the mixture are blocked with a blocking agent, and the carboxyl group is neutralized and then emulsified in water.
  • polyurethane emulsions for aqueous one-component coating agents that have undergone chain extension reaction with diamine or the like are also disclosed (see Patent Documents 4 and 5), and the storage stability and water resistance and solvent resistance of the coating are improved. .
  • the blocked isocyanate is contained in the water-dispersed resin in advance, the effective isocyanate content is restricted at the time of thermal dissociation of the block, and the improvement in performance as a coating agent or an adhesive has not been sufficiently satisfied. .
  • JP 7-188371 (Abstract and paragraphs 0011, 0015) JP 2005-522559 A (summary and claim 1) JP 10-330454 A (summary and paragraph 0018) Japanese Patent Laying-Open No. 2005-154673 (summary) JP 2005-247897 A (summary)
  • the water-based polyurethane resin coatings still have various physical properties such as durability and solvent resistance, or impact resistance and gloss as compared with organic solvent-based coatings. It cannot be said that it is sufficient, and further, performance such as water dispersibility and storage stability has not been sufficiently improved. Under such circumstances, the present inventors have developed a non-anionic (nonionic) polyisocyanate to a carboxyl group-introduced isocyanate group-terminated urethane prepolymer as an improved technique for an aqueous one-component polyurethane resin coating using a blocked isocyanate compound.
  • a polyurethane emulsion for an aqueous one-component coating agent is prepared by mixing, blocking all isocyanate groups in the mixture with a blocking agent, neutralizing carboxyl groups, emulsifying in water, and further performing chain extension reaction with diamine or the like.
  • the polyurethane emulsion for water-based one-component coating agents contains a blocked isocyanate in the water-dispersed resin in advance, so that the effective isocyanate content is restricted during thermal dissociation of the block.
  • the storage stability at room temperature and above is not sufficient A.
  • the present inventors have improved the polyurethane emulsion for the aqueous one-component coating agent to further improve various film properties, and to further improve the water dispersibility and the storage stability of the emulsion.
  • a mode in which a blocked isocyanate is contained in the water-dispersed resin, a method for imparting a water-dispersible function, a reaction condition such as a selective combination of various reaction materials and a urethanization reaction, and further conditions such as emulsification in water and chain extension The invention that improves the water dispersibility and storage stability, and improves various film performances expressed in the film near the dissociation temperature of the block body, by considering and taking into consideration, etc.
  • the present inventors further studied and tried aspects such as containing a blocked isocyanate in a water-dispersed resin and selective combinations of various reaction materials.
  • HDI polyisocyanate polyisocyanate derived from hexamethylene diisocyanate
  • MDI polyisocyanate diphenylmethane diisocyanate polyisocyanate, commonly referred to as polymeric MDI
  • physical properties such as coating film strength and chemical resistance as paints are further improved, and the impregnation property to porous inorganic base material is improved, which makes it extremely useful as a primer for the base material. It is possible to find out that there is something in the previous invention (prior application invention) This has led to the development of the present invention as a kick-related invention.
  • the basic constitution of the present invention is related to the invention of the prior application, as follows: “Polymeric MDI (a1) and nonionic polar group-containing polymer polyol (a2) are reacted and the isocyanate group is blocked with the blocking agent (C). Then, the block polyisocyanate component (A) is produced, and in the reaction system, the organic polyisocyanate (b1) is reacted with the high molecular polyol (b2) and the carboxyl group-containing anionic low molecular glycol (b3) to produce carboxyl.
  • the reaction mixture is emulsified in water, and the chain extender (E) A blocked isocyanate-containing emulsion characterized in that a highly cross-linked polyurethane resin is produced by performing a chain extension reaction with The Narubutsu. ".
  • the main further features and requirements of the basic invention in the present invention are that a nonionic polar group-containing block polyisocyanate and a carboxyl group-containing isocyanate group-terminated urethane prepolymer are used in combination.
  • a carboxyl group-containing isocyanate group-terminated urethane prepolymer was synthesized in the reaction system in which the block polyisocyanate was produced. As illustrated in FIG.
  • the nonionic polar group-containing block polyisocyanate is a core component ( Emulsion composition in which a polyurethane resin obtained by neutralizing a carboxyl group-containing isocyanate group-terminated urethane prepolymer and forming a chain is formed into a shell (outer shell portion; black background portion in the figure). It is.
  • the emulsion has a water dispersion particle size distribution of 50 to 400 nm and a block isocyanate-containing emulsion composition having a core / shell weight ratio of 50/50 to 70/30, and the emulsion particle size distribution is very small.
  • various film performances such as water dispersibility and storage stability of emulsions at room temperature or higher are sufficiently improved, and film uniformity is exhibited in the film near the dissociation temperature of the block body. Has also been improved.
  • the polymer polyol (b2) has a carbonate skeleton or a phthalate skeleton
  • the neutralizing agent is an amine compound
  • the chain extender is a polyamine compound
  • an emulsion is an aqueous one-component baking emulsion.
  • the block polyisocyanate component (A) is produced using the polymeric MDI described above in paragraph 0010, and an organic polyisocyanate is used in the reaction system.
  • the main requirement is to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (B) by reacting (b1) with a polymer polyol (b2) and a carboxyl group-containing anionic low molecular glycol (b3). It is. Furthermore, as a main application mode of the blocked isocyanate-containing emulsion composition of the present invention, the blocked isocyanate-containing emulsion composition is used as a curing agent, and the main component contains other resin components such as polyurethane resin, It is an aqueous one-component coating composition, and is an aqueous base treatment agent for porous substrates made of a blocked isocyanate-containing emulsion composition.
  • the nonionic polar group-containing isocyanate derived from the polymeric MDI is blocked to produce a block polyisocyanate, and a carboxyl group-containing isocyanate group-terminated urethane prepolymer is synthesized in the reaction system and emulsified after neutralization.
  • a carboxyl group-containing isocyanate group-terminated urethane prepolymer is synthesized in the reaction system and emulsified after neutralization.
  • the organic polyisocyanate (a1) and the nonionic polar group-containing polymer polyol (a2) are reacted, and the isocyanate group is blocked with the blocking agent (C).
  • the blocked polyisocyanate component (A) is produced by blocking
  • HDI polyisocyanate polyisocyanate derived from hexamethylene diisocyanate
  • MDI-based polyisocyanate diphenylmethane diisocyanate-based polyisocyanate, commonly referred to as polymeric MDI
  • polymeric MDI is used as the organic polyisocyanate.
  • the present invention is an invention different from the prior application invention, and further new compared to the prior application invention. It is obvious that the invention has a remarkable effect.
  • the present invention is composed of the following invention unit groups, the inventions [1] and [2] are the basic inventions, and the inventions below are the basic inventions. Is embodied or embodied. (The invention group as a whole is collectively referred to as “the present invention”.)
  • Polymeric MDI (a1) is reacted with a nonionic polar group-containing polymer polyol (a2), and an isocyanate group is blocked with a blocking agent (C) to produce a blocked polyisocyanate component (A).
  • the organic polyisocyanate (b1) is reacted with the polymer polyol (b2) and the carboxyl group-containing anionic low molecular glycol (b3) to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (B)
  • the reaction mixture was emulsified in water and subjected to chain extension reaction with the chain extender (E) to produce a highly crosslinked polyurethane resin.
  • the block isocyanate containing emulsion composition characterized by the above-mentioned.
  • Polymeric MDI (a1) is reacted with a nonionic polar group-containing polymer polyol (a2), and an isocyanate group is blocked with a blocking agent (C) to produce a blocked polyisocyanate component (A).
  • the organic polyisocyanate (b1) is reacted with the polymer polyol (b2) and the carboxyl group-containing anionic low molecular glycol (b3) to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (B), After neutralizing the carboxyl groups in the reaction system with a neutralizing agent (D), the reaction mixture is emulsified in water and subjected to chain extension reaction with polyamine (E) to produce a highly crosslinked polyurethane resin. Production of a blocked isocyanate-containing emulsion composition according to any one of [1] to [6] Law.
  • An aqueous ground treatment agent for a porous substrate comprising the blocked isocyanate-containing emulsion composition according to any one of [1] to [6].
  • An aqueous base treatment agent for a porous substrate characterized in that the blocked isocyanate-containing emulsion composition according to any one of [1] to [6] is used as a curing agent and a polyurethane resin as a main component.
  • An aqueous one-component coating composition comprising the blocked isocyanate-containing emulsion composition according to any one of [1] to [6] as a curing agent and a polyurethane resin as a main component.
  • An aqueous one-component or two-component composition comprising the blocked isocyanate-containing emulsion composition according to any one of [1] to [5] as a curing agent, a polyurethane resin as a main component, and a coating additive. Liquid baking type coating composition.
  • the emulsion particles have a fine core / shell structure, the emulsion particle size distribution is reduced, and thus (i) a uniform emulsion free of impurities, and (ii) Water dispersibility and storage stability of emulsion above room temperature are sufficiently improved. (Iii) Various coating performances such as coating strength, coating uniformity and appearance appearing near the dissociation temperature of the block can be improved. It is very useful as an aqueous paint or primer that does not use organic solvents.
  • the aqueous emulsion composition of the present invention (iv) can form a uniform film that is not affected by the environmental temperature, and (v) is aqueous, so that it is environmentally safe with respect to the atmosphere and drainage, and in the manufacturing process and enforcement. Work safety is high, and handling (handling) is also good. Furthermore, the aqueous emulsion composition of the present invention has (vi) a simple production process and good productivity, and (vii) excellent compatibility with the main agent of a coating material such as polyurethane resin. Furthermore, the present invention is (viii) a further improvement in physical properties such as coating strength and chemical resistance (organic solvent, alkali resistance and acid resistance) and drying properties as compared to the prior invention. In addition, the impregnation property, adhesion property, and water resistance to the porous inorganic base material are improved, and it is very useful as a base treatment agent (primer) for the base material.
  • a base treatment agent for the base material.
  • Blocked Isocyanate-Containing Emulsion Composition The basic composition in the present invention group, the blocked isocyanate-containing emulsion composition, is a water-based emulsion using a blocked isocyanate compound and its one-component polyurethane.
  • the blocked isocyanate-containing emulsion composition is a water-based emulsion using a blocked isocyanate compound and its one-component polyurethane.
  • the present invention is a technique for solving such conventional problems as in the prior invention.
  • the present invention basically uses a nonionic polar group-containing block polyisocyanate and a carboxyl group-containing isocyanate group-terminated urethane prepolymer mainly for the purpose of improving the storage stability and water dispersibility of the emulsion composition. Therefore, the main feature is that a carboxyl group-containing isocyanate group-terminated urethane prepolymer is synthesized in a reaction system in which a nonionic polar group-containing block polyisocyanate is produced, and emulsification and chain extension are carried out after neutralization.
  • the polymeric MDI (a1) and the nonionic polar group-containing polymer polyol (a2) are reacted, and the isocyanate group is blocked with a blocking agent (C) to produce a blocked polyisocyanate component (A).
  • the organic polyisocyanate (b1) is reacted with the polymer polyol (b2) and the carboxyl group-containing anionic low molecular glycol (b3) to obtain a carboxyl group-containing isocyanate group-terminated urethane prepolymer (B).
  • reaction mixture After the production and neutralization of the carboxyl group in the reaction system with the neutralizing agent (D), the reaction mixture is emulsified in water and subjected to chain extension reaction with the chain extender (E) to obtain a highly crosslinked polyurethane resin. It is a block isocyanate-containing emulsion composition that has been produced.
  • the block isocyanate-containing emulsion composition of the present invention has a fine core / shell structure (structure that can also be referred to as a nanocapsule).
  • the nonionic polar group-containing block polyisocyanate serves as a core component (core portion), and neutralizes the carboxyl group-containing isocyanate group-terminated urethane prepolymer.
  • the dispersion is stable in an emulsion composition in which a strong and flexible highly cross-linked anionic polyurethane having a chain extended to form a shell (outer shell portion).
  • the emulsion has a water-dispersed particle size distribution of 50 to 400 nm and a core / shell weight ratio of 50/50 to 70/30, which is a blocked isocyanate-containing emulsion composition.
  • the dispersibility and the storage stability of the emulsion above room temperature are sufficiently improved, and it does not separate over a long period of time.
  • various film performances such as film strength and film uniformity and appearance that are developed around the dissociation temperature of the block can be further improved, and a uniform film can be formed without being affected by the environmental temperature. It is also excellent in compatibility with the main ingredients of coating agents such as modified polyolefin resins.
  • coating agents such as modified polyolefin resins.
  • a nonionic polar group-containing block polyisocyanate dispersion corresponding to the prior invention described in paragraph 0006 and the like serves as a core component, and a carboxyl group-containing isocyanate group-terminated urethane.
  • the state in which the polyurethane resin obtained by neutralizing the prepolymer and extending the chain partially adheres to the periphery of the core portion is illustrated.
  • the emulsion composition of the present invention produces a uniform emulsion without impurities in the particle size (particle size) distribution state, Additional features of the present invention are also formed. This specific feature is described above as effect (i) in paragraph 0020.
  • Organic polyisocyanate (a1) As the organic polyisocyanate component (a1) used in the production of the block polyisocyanate component (A) of the present invention, specifically, polymeric MDI is exclusively used as described in paragraph 0009 and the like. That is, in the prior invention, instead of HDI polyisocyanate (polyisocyanate derived from hexamethylene diisocyanate) as the organic polyisocyanate material, MDI polyisocyanate (polymeric MDI which is diphenylmethane diisocyanate polyisocyanate) is used.
  • HDI polyisocyanate polyisocyanate derived from hexamethylene diisocyanate
  • MDI polyisocyanate polymeric MDI which is diphenylmethane diisocyanate polyisocyanate
  • Polymeric MDI is commonly used as a polyisocyanate raw material for polyurethane resins.
  • the commonly known polymeric MDI is binuclear MDI (diphenylmethane diisocyanate) and trinuclear or higher polynuclear (MDI condensation). Body)) (polyphenylene polymethylene polyisocyanate).
  • Polymeric MDI can be obtained by converting the amino group of the condensation mixture (polyamine) obtained by the condensation reaction of aniline and formalin to an isocyanate group by phosgenation, etc. By changing, the composition (nuclear distribution and isomer composition ratio) of the finally obtained polymeric MDI can be controlled.
  • Polymeric MDI (a1) used in the present invention includes reaction conditions such as a reaction liquid after conversion to an isocyanate group, a crude product obtained by removing the solvent from the reaction liquid, and a bottom liquid obtained by distilling and separating a part of MDI. Several different mixtures such as separation conditions may be used.
  • the MDI content of the polymeric MDI (a1) is 50% or less, preferably 20 to 40%. If the MDI content exceeds 50%, the average number of functional groups of the polymeric MDI is lowered, and it is difficult to obtain a film having sufficient physical properties.
  • the MDI content is determined by performing gel permeation chromatography (GPC) analysis of the polymeric MDI, and the MDI peak area ratio in the total area of the peaks of all the polymeric MDI components.
  • GPC gel permeation chromatography
  • the MDI contained in the polymeric MDI (a1) has two benzene rings and two isocyanate groups in one molecule, and is a so-called binuclear body.
  • the isomers constituting MDI are 2,2′-diphenylmethane diisocyanate (2,2′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 4,4′-diphenylmethane diisocyanate (4,4). 4′-MDI).
  • the isomer composition ratio of MDI is not particularly limited, but the 4,4′-MDI content is preferably 70% by mass or more, and preferably 90 to 99.9% by mass because the strength of the resulting coating is improved. .
  • the MDI content of polymeric MDI (a1) and the isomer composition ratio of MDI can be obtained from a calibration curve based on the area percentage of each peak obtained by GPC or gas chromatography.
  • the average number of functional groups of the polymeric MDI (a1) is 2.3 or more, and preferably the number of functional groups is 2.3 to 3.1.
  • the isocyanate content is 28 to 33% by mass, preferably 28.5 to 32.5% by mass.
  • the acidity of the polymeric MDI (a1) is preferably 0.001 to 0.2% by mass, more preferably 0.003 to 0.15% by mass. is there.
  • the acidity is a value obtained by converting an acid component that reacts with alcohol at room temperature and liberated into hydrogen chloride, and is a value measured by JISK-1603.
  • a polyisocyanate other than the polymeric MDI can be used in combination.
  • urethanized product, urea product, allophanate product, burette product, carbodiimidide product, uretoniminate product, uretdione product, isocyanurate product, tetramethylene diisocyanate obtained by reacting MDI or polymeric MDI with an active hydrogen group-containing compound Aliphatic diisocyanates such as hexamethylene diisocyanate, aliphatic diisocyanates such as 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, x
  • urethanized products obtained by reacting these isocyanates with active hydrogen group-containing compounds, urea products, allophanate products, burette products, carbodiimidate products, ureton iminate products, uretdione products, isocyanurate products, etc.
  • active hydrogen group-containing compounds urea products, allophanate products, burette products, carbodiimidate products, ureton iminate products, uretdione products, isocyanurate products, etc.
  • active hydrogen group-containing compounds urea products, allophanate products, burette products, carbodiimidate products, ureton iminate products, uretdione products, isocyanurate products, etc.
  • Nonionic polar group-containing polymer polyol (a2)
  • the polymer polyol compound forming the block polyisocyanate in the present invention uses a polyol compound containing a nonionic polar group, for example, a nonionic polar group.
  • a polyalkylene ether polyol containing a normal alkoxy polar group is used.
  • Ordinary nonionic polar group-containing polyester polyols and polycarbonate polyols are also used.
  • the polymer polyol those having a number average molecular weight of 500 to 10,000, particularly 500 to 5,000 are preferably used.
  • Block agent (C) The blocking agent (C) used in the present invention is not particularly limited, and one or more blocking agents can be appropriately selected from known ones.
  • the blocking agent include phenolic, alcoholic, active methylene, mercaptan, acid amide, lactam, acid imide, imidazole, urea, oxime, and amine compounds.
  • phenol compounds such as phenol, cresol and ethyl phenol
  • alcohol compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol
  • active methylene compounds such as dimethyl malonate and acetylacetone
  • Mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, acid amide compounds such as acetanilide and acetic acid amide, lactam compounds such as ⁇ -caprolactam and ⁇ -valerolactam, and acid imide compounds such as succinimide and maleic acid imide Oxime compounds such as acetoaldoxime, acetone oxime, methyl ethyl ketoxime, and amine compounds such as diphenylaniline, aniline, ethyleneimine Can be mentioned.
  • methyl ethyl ketoxime, ⁇ -caprolactam, and 2-ethyl hexanol are preferable from the viewpoint of easy availability and workability.
  • Organic polyisocyanate (b1) As the organic polyisocyanate component (b1) used in the production of the carboxyl group-containing isocyanate group-terminated urethane prepolymer (B) of the present invention, a bifunctional organic diisocyanate compound is preferably used. The usual ones are used and are not particularly defined. In order to avoid yellowing of the coating film due to ultraviolet rays, aliphatic or alicyclic diisocyanates are preferred over aromatic diisocyanates.
  • tetramethylene diisocyanate hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene-1
  • Aliphatic diisocyanates such as 6-diisocyanate and 2,4,4-trimethylhexamethylene-1,6-diisocyanate are exemplified, and isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethylxylylene diene
  • Illustrative are alicyclic diisocyanates such as isocyanate.
  • diisocyanates are used individually by 1 type or in mixture of 2 or more types. Further, such adduct modified products, carbodiimide modified products, allophanate modified products, burette modified products, uretdione modified products, uretoimine, such as allophanate modified polyisocyanates obtained from hexamethylene diisocyanate and monools having 1 to 6 carbon atoms. Modified products, isocyanurate modified products, and the like can also be used.
  • aromatic diisocyanates 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4′-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, m-phenylene diisocyanate, p -Phenylene diisocyanate, naphthylene-1,4-diisocyanate and the like are exemplified.
  • Polymer polyol (b2) The polymer polyol (b2) used in the production of the carboxyl group-containing isocyanate group-terminated urethane prepolymer in the present invention is a polyester polyol or polyester amide having a normal number average molecular weight of 500 to 10,000, preferably 500 to 5,000. Polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols and the like are used, and these polymer polyols may be used in combination. In consideration of the water resistance of the shell portion, the polymer polyol preferably has a carbonate skeleton or a phthalate skeleton.
  • Polyester polyols and polyester amide polyols include polycarboxylic acid derivatives such as polycarboxylic acids, acid esters, acid anhydrides, acid halides, low molecular polyols having a number average molecular weight of less than 500, low molecular polyamines, low molecular amino alcohols, and the like. It is obtained by the reaction of
  • Carboxyl group-containing anionic low molecular weight glycol (b3) The carboxyl group-containing anionic low molecular weight glycol used in the production of the carboxyl group-containing isocyanate group-terminated urethane prepolymer (B) of the present invention is obtained by reacting the active hydrogen groups of the hydroxyl groups at both ends with isocyanate groups. Since it is incorporated into the main chain and the free carboxyl group is hydrophilic, it acts to increase the water dispersibility of the prepolymer. The carboxyl group is neutralized to increase the hydrophilicity.
  • carboxyl group-containing anionic low molecular weight glycol examples include dimethylolpropionic acid and dimethylolbutanoic acid having two terminal hydroxyl groups, other reaction products of polyamine and acid anhydride, dimethylolpropionic acid and dimethylol. Lactone adducts and the like using butanoic acid as an initiator are also used as appropriate.
  • Neutralizing agent (D) A normal thing is arbitrarily used as a neutralizing agent of this invention.
  • organic amines such as ethylamine, trimethylamine, triethylamine, triisopropylamine, triethanolamine, triisopropanolamine, morpholine, N-methylmorpholine are preferably used, and inorganic alkalis such as sodium hydroxide and potassium hydroxide, and ammonia are also illustrated.
  • a highly volatile one that is easily dissociated by heat or an amino alcohol that reacts with a polyisocyanate curing agent is more preferred.
  • Chain extender is not particularly limited, but the diamine or polyamine compound is more advantageous in physical properties such as water resistance, solvent resistance, and stain resistance because it is more highly crosslinked than a diol compound as a chain extender.
  • Curing catalyst and curing agent Resinization catalyst as a curing catalyst (polymerization catalyst) for urethane reaction is used as necessary, and is a metal catalyst such as dibutyltin dilaurate or zinc naphthenate or triethylenediamine. Ordinary curing catalysts such as amine catalysts such as N-methylmorpholine are used, and the reaction rate can be increased and the reaction temperature can be lowered.
  • a curing agent for curing the polyurethane resin hexamethylene diisocyanate (H DI) or isophorone diisocyanate (IPDI) is used as a trimer or adduct having 3 or more NCO groups in one molecule.
  • the method for producing a block isocyanate-containing emulsion composition basically includes polymeric MDI (a1) and nonionic polar group-containing polymer polyol (a2). ), And the isocyanate group is blocked with a blocking agent (C) to produce a blocked polyisocyanate component (A).
  • organic polyisocyanate (b1), polymer polyol (b2) and carboxyl The group-containing anionic low molecular glycol (b3) was reacted to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (B), and the carboxyl group in the reaction system was neutralized with the neutralizing agent (D). After that, the reaction mixture is emulsified in water and added to the chain extender (E) polyamine. By performing a chain extension reaction.
  • the non-ionic polar group-containing isocyanate is blocked to form a blocked polyisocyanate, and the emulsion particles have a fine core / shell structure due to the basic requirement of synthesizing the carboxyl group-containing isocyanate group-terminated urethane prepolymer in the reaction system.
  • the effects of the inventions (i) to (iii) described in paragraph 0020 are brought about.
  • the blocking reaction can be carried out according to the usual blocking reaction conditions of 20 to 100 ° C, preferably 30 to 90 ° C.
  • a known urethanization catalyst may be used.
  • the blocking rate is preferably 20 mol% or more, particularly preferably 30 to 50 mol%. If the blocking rate is too low, the strength and durability of the coating tends to be insufficient.
  • a known urethanization catalyst may be used during the production of the carboxyl group-containing isocyanate group-terminated urethane prepolymer.
  • the reaction temperature is preferably 0 to 100 ° C., particularly preferably 20 to 90 ° C.
  • organic solvent examples include aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, ketone solvents such as acetone and methyl ethyl ketone, and acetic acid.
  • Ester solvents such as ethyl and butyl acetate, glycol ether ester solvents such as ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate, glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dibutyl ether and propylene glycol dibutyl ether used.
  • Neutralization can be performed according to normal neutralization reaction conditions of 20 to 50 ° C. with any neutralizing agent described in paragraph 0041.
  • Aqueous polyurethane resin emulsion coating composition (1) Main agent and curing agent
  • the aqueous polyurethane resin coating composition in the present invention is an application mode of the blocked isocyanate-containing emulsion composition which is the basic invention in the present invention, and is used as a coating agent (paint).
  • the coating composition is basically composed of a main agent and a curing agent, and a blocked isocyanate-containing emulsion composition is used as a curing agent, and a normal polyurethane resin or modified polyolefin resin is appropriately used as the main agent. Although it is used in a one-component type in which the main agent and the curing agent are mixed in advance, it may be a two-component type in which the main agent and the curing agent are mixed at the time of use in coating construction.
  • the coating composition is applied to various base materials such as metal, plastic, wood, and inorganic materials as a coating agent, and then the coating layer is heated to form a block body. Dissociates, and a high crosslinking reaction occurs between the isocyanate group and the active hydrogen, which is cured and baked.
  • additives In order to enhance physical properties and add various other physical properties, as various additives, arbitrarily, flame retardants, plasticizers, antioxidants, ultraviolet absorbers, dyes, pigments, Fillers, internal mold release agents, reinforcing materials, matting agents, conductivity imparting agents, charge control agents, antistatic agents, lubricants, and other processing aids can be used.
  • Aqueous surface treatment agent for porous substrate (1) Surface treatment agent The aqueous surface treatment agent for porous substrate in the present invention is a second application mode of the block isocyanate-containing emulsion composition which is the basic invention in the present invention. It is used as an aqueous surface treatment agent (primer) for porous substrates, particularly for inorganic porous substrates.
  • a blocked isocyanate-containing emulsion composition alone or a mixture of a polyurethane resin as a main component and a blocked isocyanate-containing emulsion composition as a curing agent is used as a porous substrate, particularly a slate. It is applied as an undercoat (primer) to an inorganic porous substrate such as a plate, cement plate, calcium silicate plate or gypsum plate, and the surface is sealed. Usually, since a paint or a coating is applied onto the primer, the sealing improves the workability of painting.
  • the above-mentioned inorganic porous substrate is porous and brittle, and the surface is easily powdered.
  • the alkaline substance is easily dissolved and eluted on the surface to be coated.
  • the paint film is peeled off when the curing tape is removed or when water penetrates or freezes and melts over time, and the surface of the paint film is whitened due to dissolution and dissolution of alkaline substances in the base material.
  • coating process of a surface treating agent like the blocked isocyanate containing emulsion composition of this invention becomes inevitable.
  • the blocked isocyanate-containing emulsion composition of the present invention is practically higher in impregnation and adhesion to the surface of the porous substrate than demonstrated in ordinary resin-based emulsions, as demonstrated in the examples below. It is rich in nature. Further, as demonstrated in the examples described later, the blocking property (adhesiveness) immediately after drying is low and easy to handle, and the water resistance after aging is also rich.
  • Aqueous polyurethane dispersion A (manufactured by Nippon Polyurethane Industry Co., Ltd., polycarbonate-based non-yellowing type; viscosity 60 mPa ⁇ s (25 ° C.), non-volatile content 35 wt%, dispersed particle size 70 nm) 100 g and each emulsion listed in Table 1.
  • a leveling agent manufactured by Polyflow KL • 280, Kyoei Chemical Co., Ltd.
  • Comparative Intermediate A-1 Emulsion without a polyurethane resin (shell component) obtained by neutralizing a carboxyl group-containing isocyanate group-terminated urethane prepolymer and extending the chain
  • Comparative Intermediate A-2 Block Emulsion without polyisocyanate component (core component)
  • Comparative composition A Simple mixture of comparative intermediate A-1 and comparative intermediate A-2
  • Comparative composition B Emulsion of prior invention without using polymeric MDI is there.
  • Comparative Composition A which does not produce a core / shell in the same reaction system, cold blend
  • precipitation occurs
  • Comparative Intermediate A-1 does not have a shell portion.
  • Two layers of separation occur, each lacking water dispersibility because the average particle size of the emulsion is not micro.
  • Table 2 in Examples 1 to 3 corresponding to the aqueous one-component coating composition of the present invention, the performance such as appearance, MEK rubbing (organic solvent resistance), and chemical resistance as a coating film is well expressed. ing.
  • the average particle size of the emulsion is the smallest compared to Examples 1 and 3, so the appearance is clear and not matte.
  • the drying time is slightly shorter (5 minutes), so the organic solvent resistance is , 2 (drying time 15 minutes) is slightly lower, but quick drying performance is apparent.
  • Comparative Example 1 uses Comparative Composition A (cold blend emulsion that does not produce a core and shell in the same reaction system), so that coating film cracking occurs even when applied, and coating film performance cannot be measured. It cannot be used as a paint. Since Comparative Examples 2 and 3 use Comparative Composition B (emulsion according to the invention of the prior application that does not use polymeric MDI), performances such as MEK rubbing and chemical resistance are somewhat inferior to those of the present invention. Rather, it should be said that the emulsion of the present invention is more excellent than the emulsion of the invention of the prior application having various performances.
  • the present invention has a remarkable superiority as compared with the prior art.
  • the chemical resistance of the coating film as a coating material is maintained while maintaining the various performances compared to the prior application invention which is excellent in various performances by pushing mainly the polymeric MDI.
  • Further improvements in physical properties such as (organic solvent resistance, alkali resistance and acid resistance), and improved impregnation, adhesion and water resistance to the porous inorganic base material. Since the present invention is very useful as a (primer), the present invention is an invention different from the invention of the prior application, and an invention that exhibits further new and remarkable effects as compared with the invention of the prior application. It can be said that it has been clarified.
  • the emulsion particles have a fine core / shell structure, the emulsion particle size distribution is reduced, and thus (i) a uniform emulsion free of impurities, and (ii) Water dispersibility and storage stability of emulsion above room temperature are sufficiently improved.
  • Various coating performances such as coating strength, coating uniformity and appearance appearing near the dissociation temperature of the block can be improved.
  • Impregnation, adhesion and water resistance to a porous inorganic base material are improved, and it is industrially very useful as a water-based paint or a base treatment agent (primer) which does not use an organic solvent.

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Abstract

La présente invention concerne une émulsion de polyuréthane pour utilisation dans des matériaux de revêtement de résine polyuréthane à base aqueuse à un composant utilisant un composé isocyanate bloqué qui est améliorée de manière à améliorer plus avant les performances de film de revêtement de matériaux de revêtement de l'émulsion. Cette émulsion est également utilisée en tant que couche primaire. La présente invention concerne en outre une composition d'émulsion contenant un isocyanate bloqué qui est produite par : réaction de MDI polymère (a1) avec un polyol à poids moléculaire élevé (a2) contenant un groupe polaire non ionique ; blocage des groupes isocyanate avec un agent bloquant (C) pour produire un composant polyisocyanate bloqué (A) ; réaction d'un polyisocyanate organique (b1) avec un polyol à poids moléculaire élevé (b2) et un glycol anionique carboxylé à faible poids moléculaire (b3) dans le système de réaction résultant pour produire un prépolymère d'uréthane à terminaison isocyanate carboxylé (B) ; neutralisation des groupes carboxy avec un agent neutralisant (D) ; puis émulsification du mélange de réaction dans l'eau ; et ensuite utilisation d'un extenseur de chaîne (E) pour mener une réaction d'extension de chaîne et produire ainsi une résine polyuréthane hautement réticulée.
PCT/JP2009/053707 2008-03-14 2009-02-27 Composition d'émulsion contenant un isocyanate bloqué, procédé pour produire celle-ci, couche primaire à base aqueuse pour substrat poreux, et composition de revêtement au four à base aqueuse WO2009113412A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2561986A1 (fr) * 2010-04-22 2013-02-27 Mitsubishi Plastics, Inc. Film polyester stratifié
EP2716675A1 (fr) * 2011-05-31 2014-04-09 UBE Industries, Ltd. Dispersion de résine polyuréthane aqueuse, et composition pour revêtement comprenant celui-ci
JP2015096930A (ja) * 2013-11-17 2015-05-21 槌屋ティスコ株式会社 蛇行防止部材及びその製造方法
JP2015120821A (ja) * 2013-12-24 2015-07-02 東ソー株式会社 水性一液焼き付け被覆塗料用組成物、及び該組成物を用いた被覆材料
JP2016540659A (ja) * 2013-09-30 2016-12-28 コーロン インダストリーズ インク 光学フィルム
CN112661933A (zh) * 2020-12-09 2021-04-16 武汉弘毅共聚新材料科技有限公司 一种可反应性水性聚氨酯的制备方法
WO2021256224A1 (fr) * 2020-06-19 2021-12-23 東洋紡株式会社 Film de polyester multicouche
JP2022540688A (ja) * 2019-07-16 2022-09-16 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 一液型のポリウレタン分散体、その製造及び使用
WO2023277081A1 (fr) * 2021-06-30 2023-01-05 旭化成株式会社 Composition de polyisocyanate séquencé, composition de résine, film de résine, et corps stratifié

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JP2005247897A (ja) * 2004-03-01 2005-09-15 Nippon Polyurethane Ind Co Ltd 水性一液コーティング剤用ポリウレタンエマルジョンの製造方法
WO2008020492A1 (fr) * 2006-08-18 2008-02-21 Nippon Polyurethane Industry Co., Ltd. Composition d'émulsion contenant des isocyanates bloqués, son procédé de production et compositions servant à durcir des peintures ou des adhésifs

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JPS6131422A (ja) * 1984-07-24 1986-02-13 Nippon Polyurethan Kogyo Kk 水分散性ブロツクイソシアネ−トの製造法
JPH07188371A (ja) * 1993-12-28 1995-07-25 Mitsui Toatsu Chem Inc 多官能プレポリマーを用いた水性ウレタン樹脂組成物
JP2003055431A (ja) * 2001-08-17 2003-02-26 Nippon Polyurethane Ind Co Ltd 水性ポリウレタン系エマルジョン、並びにこれを用いた水性接着剤及び水性塗料
JP2005154674A (ja) * 2003-11-28 2005-06-16 Nippon Polyurethane Ind Co Ltd 水性一液コーティング剤用ポリウレタンエマルジョンの製造方法
JP2005247897A (ja) * 2004-03-01 2005-09-15 Nippon Polyurethane Ind Co Ltd 水性一液コーティング剤用ポリウレタンエマルジョンの製造方法
WO2008020492A1 (fr) * 2006-08-18 2008-02-21 Nippon Polyurethane Industry Co., Ltd. Composition d'émulsion contenant des isocyanates bloqués, son procédé de production et compositions servant à durcir des peintures ou des adhésifs

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2561986A1 (fr) * 2010-04-22 2013-02-27 Mitsubishi Plastics, Inc. Film polyester stratifié
EP2561986A4 (fr) * 2010-04-22 2014-01-15 Mitsubishi Plastics Inc Film polyester stratifié
US9169420B2 (en) 2011-05-31 2015-10-27 Ube Industries, Ltd. Aqueous polyurethane resin dispersion and coating composition comprising the same
EP2716675A4 (fr) * 2011-05-31 2014-11-26 Ube Industries Dispersion de résine polyuréthane aqueuse, et composition pour revêtement comprenant celui-ci
EP2716675A1 (fr) * 2011-05-31 2014-04-09 UBE Industries, Ltd. Dispersion de résine polyuréthane aqueuse, et composition pour revêtement comprenant celui-ci
JP2016540659A (ja) * 2013-09-30 2016-12-28 コーロン インダストリーズ インク 光学フィルム
JP2015096930A (ja) * 2013-11-17 2015-05-21 槌屋ティスコ株式会社 蛇行防止部材及びその製造方法
JP2015120821A (ja) * 2013-12-24 2015-07-02 東ソー株式会社 水性一液焼き付け被覆塗料用組成物、及び該組成物を用いた被覆材料
JP2022540688A (ja) * 2019-07-16 2022-09-16 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 一液型のポリウレタン分散体、その製造及び使用
JP7433411B2 (ja) 2019-07-16 2024-02-19 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 一液型のポリウレタン分散体、その製造及び使用
WO2021256224A1 (fr) * 2020-06-19 2021-12-23 東洋紡株式会社 Film de polyester multicouche
KR20230029591A (ko) 2020-06-19 2023-03-03 도요보 가부시키가이샤 적층 폴리에스테르 필름
CN112661933A (zh) * 2020-12-09 2021-04-16 武汉弘毅共聚新材料科技有限公司 一种可反应性水性聚氨酯的制备方法
WO2023277081A1 (fr) * 2021-06-30 2023-01-05 旭化成株式会社 Composition de polyisocyanate séquencé, composition de résine, film de résine, et corps stratifié

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